WO2000065287A1 - Multistage rapid product refrigeration apparatus and method - Google Patents
Multistage rapid product refrigeration apparatus and method Download PDFInfo
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- WO2000065287A1 WO2000065287A1 PCT/US1999/018561 US9918561W WO0065287A1 WO 2000065287 A1 WO2000065287 A1 WO 2000065287A1 US 9918561 W US9918561 W US 9918561W WO 0065287 A1 WO0065287 A1 WO 0065287A1
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- refrigerant
- refrigeration
- thermal reservoir
- loop
- heat
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D3/00—Devices using other cold materials; Devices using cold-storage bodies
- F25D3/005—Devices using other cold materials; Devices using cold-storage bodies combined with heat exchangers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B25/00—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00
- F25B25/005—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00 using primary and secondary systems
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D16/00—Devices using a combination of a cooling mode associated with refrigerating machinery with a cooling mode not associated with refrigerating machinery
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D17/00—Arrangements for circulating cooling fluids; Arrangements for circulating gas, e.g. air, within refrigerated spaces
- F25D17/02—Arrangements for circulating cooling fluids; Arrangements for circulating gas, e.g. air, within refrigerated spaces for circulating liquids, e.g. brine
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2303/00—Details of devices using other cold materials; Details of devices using cold-storage bodies
- F25D2303/08—Devices using cold storage material, i.e. ice or other freezable liquid
- F25D2303/084—Position of the cold storage material in relationship to a product to be cooled
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2331/00—Details or arrangements of other cooling or freezing apparatus not provided for in other groups of this subclass
- F25D2331/80—Type of cooled receptacles
- F25D2331/803—Bottles
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2331/00—Details or arrangements of other cooling or freezing apparatus not provided for in other groups of this subclass
- F25D2331/80—Type of cooled receptacles
- F25D2331/805—Cans
Definitions
- the present invention relates to multistage refrigeration systems and processes, and in particular to the use of a thermal reservoir in an intermediate refrigeration loop for storing thermal reservoir material in heat exchange relation with the refrigerant in that intermediate refrigeration loop.
- a refrigeration system provides a means for transferring heat away from an object or space to be cooled.
- the heat transfer agents or media used in refrigeration systems known in the art include water, aqueous brines, alcohols, glycols, ammonia, hydrocarbons, ethers, and various halogen derivatives of these materials. While many of these materials provide effective heat transfer media under certain conditions, physical considerations eliminate many of them from use in various settings.
- the primary refrigerant loop running through the compressor is segregated from the secondary refrigerant loop used to cool the goods being refrigerated, the primary refrigerant loop may utilize ammonia or other high efficiency refrigerants that are unsuitable for use as direct refrigerants in many applications.
- the present invention provides a multistage refrigeration system.
- the system has a first refrigeration loop with a first refrigerant disposed therein, a second refrigeration loop with a second refrigerant disposed therein, and a third refrigeration loop with a third refrigerant disposed therein.
- the system includes a first heat exchanger for transferring heat from the second refrigerant to the first refrigerant, and a second heat exchanger for transferring heat from the third refrigerant to the second refrigerant.
- a thermal reservoir is provided in the second refrigeration loop. The thermal reservoir stores a thermal reservoir material in heat exchange relation with the second refrigerant.
- the second refrigerant is selected from the group consisting of perfluorocarbons (PFCs), perfluoropolyethers (PFEs), hydro fluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrochlorofluorocarbons (HCFCs), hydrochlorofluoroethers (HCFEs), chlorofluorocarbons (CFCs), hydrochlorocarbons (HCCs), hydrobromocarbons (HBCs), fluorinated compounds containing at least one aromatic moiety, and perfluoroiodides (PFIs).
- PFCs perfluorocarbons
- PFEs perfluorocarbons
- HFCs hydro fluorocarbons
- HFEs hydrofluoroethers
- HCFCs hydrochlorofluorocarbons
- HCFEs hydrochlorofluoroethers
- HCCs hydrochlorocarbons
- HBCs hydro
- the thermal reservoir has a freezing point ranging from about 0° to -40 °C, and more preferably, a freezing point of about -7 °C.
- the third refrigerant is preferably air.
- the refrigeration system further includes a conduit in the second refrigeration loop for diverting the second refrigerant to selectively bypass the second heat exchanger.
- the process further includes cooling a thermal reservoir material disposed in a thermal reservoir in the second refrigerant loop until a desired temperature for the thermal reservoir material is attained by transferring heat from the thermal reservoir material to the second refrigerant in the thermal reservoir, and cooling the second refrigerant by transferring heat retained therein from the third refrigerant to the thermal reservoir material in the thermal reservoir.
- the third refrigerant loop includes a cooling chamber, and the process further comprises transferring heat from objects in the cooling chamber to the third refrigerant.
- the process includes cooling the objects in the cooling chamber to a predetermined final temperature, removing the objects from the cooling chamber at a desired removal rate, and pulsing the rate of circulation of the second refrigerant through the second refrigeration loop to maintain a suitable temperature in the cooling chamber until all of the objects have been removed therefrom.
- the process includes excluding the second heat exchanger from the second refrigerant flow until the thermal reservoir material has reached the desired temperature.
- the thermal reservoir material undergoes a phase change from a liquid state to a solid state as it approaches the desired temperature while heat is transferred from the thermal reservoir material to the second refrigerant.
- FIG. 2 is a schematic perspective illustration of a thermal reservoir suitable for use in the multistage refrigeration system of FIG. 1.
- second refrigeration loop refers to the path over which a second refrigerant medium travels while it is being cycled between the third refrigeration loop and the primary refrigeration loop.
- second refrigerant medium or “second refrigerant” refers to the heat transfer medium in the second refrigeration loop.
- the first refrigeration loop 12 is defined by a first refrigerant line 18 which connects, in series, a compressor 20, ambient air heat exchanger 22, expansion valve 24 and first heat exchanger 26.
- a first or primary refrigerant medium is circulated through the first refrigerant line 18. After being warmed in the first heat exchanger 26, the first refrigerant medium has heat extracted therefrom in the compressor 20 and ambient heat air exchanger 22, with that heat being expelled to the environment. In the process, the first refrigerant medium is liquified and cooled. The first refrigerant medium is then expanded (via expansion valve 24) and returned to the first heat exchanger 26.
- the thermal reservoir 32 in the second refrigeration loop 14 is illustrated in FIG. 2.
- the thermal reservoir 32 defines an enclosure that includes serpentine tubing 44 throughout which allows the second refrigerant medium to traverse the interior of the thermal reservoir 32.
- the second refrigerant medium enters the serpentine tubing 44 through an inlet 45 and exits the serpentine tubing 44 through an outlet 46 (to return to the second refrigerant line 28).
- the serpentine tubing 44 passes through a plurality of heat exchange fins 47 disposed within the thermal reservoir
- the thermal reservoir 32 includes a reservoir or chamber 50 which includes the tubing 44 and fins 47 therein.
- a thermal reservoir material 52 is also resident within the chamber 50.
- the thermal reservoir 32 is designed to accommodate the thermal reservoir material 52 in a liquid state (at a temperature above its freezing point) and in a solid state (at a temperature below its freezing point).
- the thermal reservoir material 52 is illustrated in its solid state as at 54 in FIG. 2.
- Additives such as salts or glycols can be mixed with the water to reduce its freezing point, for example, down to below 0 °F (-18 °C), though the resultant heat storage capacity of the thermal reservoir is decreased.
- mixtures of water with salts tends to maintain the desired hard, crystalline structure of the frozen water mixture and yet maintain 70 to 80 percent of the heat storage capacity.
- mixtures of water with glycols, such as propylene glycol tend to freeze to a glassy state, which removes about half of the heat storage capacity.
- the water/glycol mixtures tend not to have a crisp melting point, but have a range of melting temperatures as energy is added to the reservoir.
- non-aqueous materials or mixtures can be employed, such as FLUORINERTTM FC-70 fluid, which has a melting point of -25 °C (available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota).
- the thermal reservoir 32 is designed to act as a heat sink. To prepare for quickly cooling products in the cooling chamber 42, the thermal reservoir material 52 is cooled, even possibly to a point where it undergoes a phase change from a liquid state to a solid state.
- the thermal reservoir material 52 is a high heat capacity liquid such as the type of salt and water mixture noted above.
- the thermal reservoir 32 is cooled by circulating the second refrigerant medium through the second refrigeration loop 14, from the first heat exchanger 26 through the thermal reservoir 32.
- the tubing 44 and fins 47 define a heat exchanger within the thermal reservoir used to cool the thermal reservoir material 52 as the coolant (second refrigerant medium) passes through the thermal reservoir 32.
- the proportion of water and freezing point depression that is, salt
- the cooling time for the thermal reservoir material 52 could take several hours, and is primarily a function of the capacity of the compressor 20 in the first refrigeration loop 12 and the size of the thermal reservoir 32.
- air (the third refrigerant medium) is circulated through the third refrigeration loop 16 by the blower 40, absorbs heat from the product to be cooled in the cooling chamber 42, and is discharged into the second heat exchanger 34. Heat from the air is transferred through the second heat exchanger 34 into the second refrigerant medium in the second refrigerant line 28. The cooled air continues circulation in the third refrigerant line 38 to again remove heat from the relatively warmer products in the cooling chamber 42. The second refrigerant is pumped from the second heat exchanger 44 through the first heat exchanger 26 and into the thermal reservoir 32.
- the circulation rate of the second refrigerant medium can be stopped or pulsed to maintain the temperature in the cooling chamber 42 until all of the product is removed therefrom.
- the primary refrigeration loop 12 operates (if at all) on a minimal basis due to the presence of the thermal reservoir 32. This conserves a significant amount of energy. Should the thermal reservoir material 52 provide, after time, an insufficient heat sink for the second refrigerant medium, the primary refrigeration loop 12 is activated to chill the second refrigerant medium as it traverses the first heat exchanger 26.
- circulation of the second refrigerant medium in the second refrigeration loop 14 is switched to bypass the second heat exchanger.
- the second refrigerant medium thus circulates from the thermal reservoir
- Suitable secondary refrigerants for use in this invention include organic or inorganic liquids having a boiling point ranging from about 15 °C to about 200 °C, preferably ranging from about 50 °C to about 110 °C, and a freezing point ranging from about 0 °C to about -150 °C.
- Such liquids include but are not limited to aqueous brines, non-halogenated organic derivatives, and various halogenated (that is, fluorine- and/or chlorine-substituted) organic derivatives.
- halogenated organic derivatives that is, fluorine- and/or chlorine-substituted
- aqueous brine is very corrosive to the metal (especially ferrous) components of the system, necessitating the incorporation of a toxic corrosion inhibitor.
- Water without added salt could be used as a secondary loop refrigerant only when the reservoir temperature is kept above the freezing point of water (32 °F, 0 °C).
- the reservoir temperature preferably is maintained at or near 20 °F (-7 °C), thus necessitating the addition of a suitable salt.
- non-halogenated organic derivatives include but are not limited to methyl alcohol and its aqueous solutions, ethyl alcohol and its aqueous solutions, isopropyl alcohol and its aqueous solutions, ethylene glycol and its aqueous solutions, propylene glycol and its aqueous solutions, TYFOXITTM 1.15 and TYFOXITTM 1.21 (inhibited alkali ethanate solutions, available from Tyforop Chemie GmbH, Hamburg, Germany), UCONTM fluids
- THERMINOLTM LT fluid alkylbenzene, C10H14, available from Solutia
- SANTOTHERMTM 60 fluid available from Solutia, Inc.
- ISOBARTM M fluid hydrocarbon mixture, available from Exxon Corp., New York, New York
- MARLOTHERMTM L available from H ⁇ ls Aktiengesellschaft, Marl, Germany
- BAYSILONTM M3 fluid polydimethylsiloxane, available from Bayer Corp., Pittsburgh,
- Halogenated organic derivatives performing satisfactorily as secondary refrigerants include perfluorocarbons (PFCs), perfluoropolyethers (PFEs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrochlorofluorocarbons (HCFCs), hydrochlorofluoroethers (HCFEs), chlorofluorocarbons (CFCs), hydrochlorocarbons (HCCs), fluorinated compounds containing at least one aromatic moiety, and perfluoroiodides (PFIs).
- PFCs perfluorocarbons
- PFEs perfluoropolyethers
- HFCs hydrofluorocarbons
- HFEs hydrofluoroethers
- HCFCs hydrochlorofluorocarbons
- HCFEs hydrochlorofluoroethers
- CFCs chlorofluorocarbons
- HCCs hydrochlorocarbons
- liquid CFCs such as CFC-113 (CCI2F2CCI2F2) and CFC-11 (CCI3F) were perhaps ideal candidates for secondary refrigerants, exhibiting excellent performance, low cost and no toxicological or safety drawback.
- CFCs have been legislated out of most commercial use situations due to their proven degradation of the stratospheric ozone layer.
- Useful PFCs include perfluorinated liquids which can be single compounds but usually will be a mixture of such compounds.
- the PFCs have molecular structures which can be straight-chained, branched-chained or cyclic, or a combination thereof, such as perfluoroalkylcycloaliphatic, are fluorinated up to at least 95 molar percent substitution of the carbon chain, and are preferably free of ethylenic unsaturation.
- the skeletal chain of the molecular structure can contain catenary (that is, "in-chain”) oxygen, trivalent nitrogen or hexavalent sulfur heteroatoms bonded only to carbon atoms, such heteroatoms providing stable linkages between fluorocarbon groups and not interfering with the inert character of the liquid.
- the inert perfluorochemical liquid will preferably have about 6 to about 18 carbon atoms, the maximum number being dictated by the desired boiling point.
- Useful PFCs include perfluoro-4-methylmorpholine, perfluorotriethylamine, perfluoro-2-ethyltetrahydrofuran, perfluoro-2-butyltetrahydrofuran, perfluorohexane, perfluoro-4-isopropylmorpholine, perfluorodibutyl ether, perfluoroheptane, perfluorooctane, perfluorotripropylamine, perfiuorononane, perfluorotributylamine, perfluorotriamylamine, perfluorotrihexylamine, perfluorodihexyl ether, perfluoro[2- (diethylamino)ethyl-2-(N-morpholino) ethyl] ether, perfluorotetrahydrophenanthrene, and mixtures thereof.
- Preferred inert fluorochemical liquids include perfluorotributylamine, perfluorotriamylamine, perfluorohexane, perfluoro-2-butyltetrahydrofuran, perfluoroheptane, perfluorooctane, and mixtures thereof, especially perfluoroheptane and perfluorooctane.
- Commercially available PFCs useful in this invention include FLUORINERTTM liquids, for example, FC-40, FC-43, FC-70, FC-71, FC-72, FC-75, FC- 77 and FC-84, described in the 1990 product bulletin #98-0211-5347-7(101.5) NPI,
- Useful HFCs include compounds having more than approximately 5 molar percent fluorine substitution, or less than 95 molar percent fluorine substitution, based on the total number of hydrogen and fluorine atoms bonded to carbon, and specifically excludes PFCs, PFEs, CFCs, HCFCs and HCFEs.
- Useful HFCs can be selected from:
- Useful HFCs of Formula I include CH 2 FCF 2 CFH2, CF 2 HCH 2 CF 3 , CF 3 CH 2 CF 2 H and
- Useful HFCs of Formula II include CHF 2 (CF 2 )2CF H, CF3CF2CH2CH2F,
- Useful HFCs of Formula III include CH3CHFCH2CF2CF3, CF3CH2CF2CH2CF3, CF3CHFCHFCF2CF3, CH3CHFCHFCF2CF3, CF3CH2CH2CF2CF3, CH3CHFCF2CF2CF3, CF3CF2CF2CH2CH3, CH3CF2CF2CF3 CF3CH2CHFCH2CF3, CH2FCF2CF2CF3, CF3CH2CF2CH2CH2F, CHF2CF2CF2CF3, CH 3 CF(CF 2 H)CHFCHF 2 , CH 3 CF(CHFCHF 2 )CF 3 , CH 3 CH(CF 2 CF3)CF3, CHF 2 CH(CHF2)CF 2 CF3, CHF 2 CF(CHF2)CF 2 CF3 and CHF 2 CF 2 CF(CF 3 )2.
- Useful HFCs of Formula IV include
- Useful HFCs of Formula V include (CF 3 CH 2 )2CHCF 3 , CH 3 CH 2 CFHCFHCF 2 CF3, CH3CHFCF2CHFCHFCF3, CH2FCHFCH2CF2CHFCF3, CF2HCHFCF2CF2CHFCF2H,
- CH2FCF2CF2CF2CF2CF2CF2H CHF2CF2CF2CF2CHF2, CHF2CF2CF2CF3, CH 3 CH(CHFCH2CF 3 )CF3, CH 3 CF(CF 2 H)CHFCHFCF 3 , CH 3 CF(CF 3 )CHFCHFCF3, CH 3 CF2C(CF3)2CF 2 CH3, CH 3 CF(CF3)CF2CF 2 CF3, CHF2CF 2 CH(CF3)CF 2 CF3 and CHF 2 CF2CF(CF3)CF 2 CF3.
- Useful HFCs of Fo ⁇ nula VII include CH3CH2CH2CH2CF2CF2CF2CF3, CH 3 (CF 2 )6CH 3 , CHF 2 CF(CF3)(CF 2 )4CHF2, CHF 2 CF(CF3)(CF 2 )4CHF 2 ,
- the HFC can be used alone, as a mixture of two or more HFCs, or as a mixture with another secondary loop refrigerant.
- Useful commercially available HFCs include VERTRELTM fluids (available from E. I duPont de Nemours and Co.) and ZEORORATM fluids (available from Nippon Zeon Co. Ltd., Tokyo, Japan).
- Prefe ⁇ ed HFEs include two identifiable varieties: (1) segregated HFEs, wherein ether-bonded alkyl or alkylene, etc., segments of the HFE are either perfluorinated (for example, perfluorocarbon) or non-fluorinated (for example, hydrocarbon), but not partially fluorinated; and (2) non- segregated HFEs, wherein at least one of the ether-bonded segments is neither perfluorinated nor fluorine-free but is partially fluorinated (that is, contains a mixture of fluorine and hydrogen atoms).
- segregated HFEs wherein ether-bonded alkyl or alkylene, etc., segments of the HFE are either perfluorinated (for example, perfluorocarbon) or non-fluorinated (for example, hydrocarbon), but not partially fluorinated
- non- segregated HFEs wherein at least one of the ether-bonded segments is neither perfluorinated nor fluorine-free but is partially fluorinated
- Segregated HFEs include HFEs which comprise at least one mono-, di-, or trialkoxy-substituted perfluoroalkane, perfluorocycloalkane, perfluorocycloalkyl- containing perfluoroalkane, or perfluorocycloalkylene-containing perfluoroalkane compound. These HFEs are described, for example, in WO 96/22356, and can be represented below in Formula VIII:
- x is from 1 to about 3
- Rf is a perfluorinated hydrocarbon group having a valency x, which can be straight, branched, or cyclic, etc., and preferably contains from about 3 to 12 carbon atoms, and more preferably contains from about 3 to 10 carbon atoms
- each R ⁇ is independently a linear or branched alkyl group having from 1 to about 8 carbon atoms, a cycloalkyl-containing alkyl group having from 4 to about 8 carbon atoms, or a cycloalkyl group having from 3 to about 8 carbon atoms; wherein either or both of the groups Rf and
- Rh can optionally contain one or more catenary heteroatoms; wherein the sum of the number of carbon atoms in the Rf group and the number of carbon atoms in the R ⁇ group(s) is preferably greater than or equal to 4.
- x is 1; Rf is a perfluoroalkyl comprising from about 3 to 10 carbons, optionally containing one or more heteroatoms; and R ⁇ is an alkyl group having from 1 to about 6 carbon atoms.
- Rf is a linear or branched perfluoroalkyl groups having from 3 to about 8 carbon atoms; a perfluorocycloalkyl-containing perfluoroalkyl group having from 5 to about 8 carbon atoms; or a perfluorocycloalkyl group having from about 5 to 6 carbon atoms;
- Rt ⁇ is an alkyl group having from 1 to about 3 carbon atoms; and Rf but not R ⁇ can contain one or more heteroatoms.
- Representative HFEs as described by Formula NIII include the following:
- Particularly prefe ⁇ ed segregated HFEs of Formula NIII include n-C3F ⁇ OCH3,
- HFEs include ⁇ ONECTM HFE- 8401HT and HFE-8402HT engineered fluids (available from Minnesota Mining and
- Segregated HFEs can be prepared by alkylation of perfluorinated alkoxides prepared by the reaction of a co ⁇ esponding perfluorinated acyl fluoride or perfluorinated ketone with an anhydrous alkali metal fluoride (for example, potassium fluoride or cesium fluoride) or anhydrous silver fluoride in an anhydrous polar aprotic solvent.
- anhydrous alkali metal fluoride for example, potassium fluoride or cesium fluoride
- anhydrous silver fluoride in an anhydrous polar aprotic solvent.
- a fluorinated tertiary alcohol can be allowed to react with a base (for example, potassium hydroxide or sodium hydroxide) to produce a perfluorinated tertiary alkoxide which can then be alkylated by reaction with alkylating agent, such as described in U.S. Patent No. 5,750,797.
- a base for example, potassium hydroxide or sodium hydroxide
- azeotropes and azeotrope-like compositions which are blends of segregated HFEs with organic solvents.
- azeotropes and azeotrope-like compositions consisting of blends of C4F9OCH3, C4F9OC2H5 and C3F7OCH3 with organic solvents.
- Such blends of C4F9OCH3 with organic solvents are described in PCT WO
- Useful ternary C4F9OCH3/solvent azeotropes and azeotrope-like compositions include blends of C4F9OCH3 with the following solvents pairs: trans- 1,2- dichloroethylene and alcohols having from 1 to 4 carbon atoms; trans- 1,2-dichloroethylene and partially fluorinated alcohols having 2 to 3 carbon atoms; trans- 1,2-dichloroethylene and acetonitrile; and HCFC-225 and alcohols having from 1 to 2 carbon atoms.
- Useful binary C3F7OCH3/solvent azeotropes and azeotrope-like compositions include blends of C3F7OCH3 with the following solvents: straight chain, branched chain and cyclic alkanes having from 5 to 7 carbon atoms; methyl formate; acetone; methanol; 1,1,1, 3,3, 3-hexafluoro-2-propanol; methylene chloride and trans- 1,2- dichloroethylene.
- Useful non-segregated HFEs include omega-hydrofluoroalkyl ethers such as those described in U.S. Patent No. 5,658,962 (Moore et al.) which can be described by the general structure shown in Formula IX: X-[-R f '-O] y R"H (Formula IX)
- X is either F, H, or a perfluoroalkyl group containing from 1 to 3 carbon atoms; each R2 is independently selected from the group consisting of -CF2-, -C2F4-, and
- R" is a divalent organic radical having from 1 to 6 carbon atoms, and is preferably perfluorinated; and y is an integer from 0 to 12; wherein when X is F, R" contains at least one F atom.
- Prefe ⁇ ed HFEs as described by Formula IX include C4F9OC2F4H, C4F9OC2F4H, C 6 F 13 OCF 2 H, HC 3 F 6 OC F 6 H, C 3 F 7 OCH 2 F and HCF 2 O(C2F 4 O) n (CF2 ⁇ ) m CF2H wherein m is from 0 to 2 and m is from 0 to 3, and mixtures thereof.
- Non-segregated HFEs described by Formula FX can be prepared by decarboxylation of the co ⁇ esponding precursor fluoroalkyl ether carboxylic acids and salts thereof or, preferably, the saponifiable alkyl esters thereof, as described in U.S. Patent No. 5,658,962.
- omega-hydrofluoroalkyl ethers can be prepared by reduction of a co ⁇ esponding omega-chlorofluoroalkyl ether (for example, those omega-chlorofluoroalkyl ethers described in WO 93/11868 published application), which is also described in U.S.
- Patent No. 5,658,962 Useful non-segregated (alpha-omega dihydro) HFEs are commercially available under the GALDEN HTM trade name from Ausimont Corp.
- Useful HCFEs include those described by the general structure shown in Formula X: Rf"-O-C a HbF c Cld (Formula X)
- Rf' ' is a perfluoroalkyl group preferably having at least about 3 carbon atoms, most preferably from 3 to 10 carbon atoms, and optionally containing a catenary heteroatom such as nitrogen or oxygen; "a” preferably is from about 1 to 6; “b” is at least 1 ; “c” can range from 0 to about 2; “d” is at least 1 ; and a+c+d is equal to 2b+l .
- Such HCFEs are described in PCT WO 99/14175.
- Useful HCFEs include c-CgFi J-OCHC12, c-
- CF3CF2CF2CF2OCHCI2 CF3CF2CF2OCHCI2, c-C 6 F ⁇ -CF 2 OCHCl2, c-C 6 F ⁇ - CF 2 OCH 2 Cl, (CF3)2CFCF 2 OCHClCH 3 , CF3CF2CF2CF2OCHCICH3, perfluoropiperidino-CF2CF2CF2OCHCl2, perfluoropiperidino-CF2CF2 ⁇ CH2Cl, (CF3)2CFCF(C 2 F 5 )OCH2Cl and (CF 3 )2CFCF(C 2 F5)OCHCl2.
- Suitable hydrochlorocarbons and hydrobromocarbons include HCCs and HBCs such as trans- 1,2-dichloroethylene, trichloroethylene, perchloroethylene, 1,1,1- trichloroethane and n-propyl bromide.
- Suitable fluorinated compounds containing at least one aromatic moiety include fluorinated monoalkyl-, dialkyl- and trialkyl-substituted aromatic compounds, including toluene and xylene derivatives. Prefe ⁇ ed among these compounds are fluoroalkyl substituted compounds, such as hexafluoroxylene, benzotrifluoride and p-chlorobenzotrifluoride. Such compounds are commercially available, for example, under the "OXSOL" trade name from Occidental Chemical Corp., Niagara Falls, New York.
- Suitable perfluoroiodides include PFIs such as perfluoropropyl iodide (C3F7I) and perfluorobutyl iodide (C4F9I).
- the equipment used for the blast cooling experiment was as follows:
- Refrigeration/Pump System (3/4 hp. 5700 BTU/hr (1670 W) capacity :
- Tecumseh Compressor Model AK 171 AT, 0.7 hp (520 W), 120N, 13 amp, air cooled condenser, with R-404a refrigerant (refrigerant available from E. I duPont de Nemours & Co., Wilmington, Delaware) (compressor 20); and (2) Laing Magnetic Coupled Pump, Model SM-1212-NTW, 1/12 hp (60 W), 120V, 1 amp (available from Arrow Tank and Engineering, Minneapolis, Minnesota)
- Insulated Thermal Storage System - 18 in x l8 in x l8 in (46 cm x 46 cm x 46 cm) plastic basin, insulated, with an outside galvanized sheet metal covering (reservoir chamber 50)
- Thermal reservoir material 220 lb (100 kg) of a solution consisting of 20 percent by weight of potassium formate in water (thermal reservoir material 52)
- Cooling coils (2) - the first 6.25 in high x 24 in wide x 18 in deep (16 cm high x 61 cm wide x 46 cm deep), 5 circuits, 16 passes, 3/8 in (1 cm) O.D. tubes made of copper, 4 fins/in (1.6 fins/cm); the second 6.25 in high x 24 in wide x 9 in deep (16 cm high x 61 cm wide x 23 cm deep), 5 circuits, 8 passes, 3/8 in (1 cm) O.D. tubes made of copper, 4 fins/in (1.6 fins/cm) (cooling coil or heat exchanger assemblies 66)
- the compressor 20 employed in the first refrigeration loop 12 has an energy rate removing capacity of 5700 BTU/hr (1670 W), as indicated by the data in TABLE 1 and the manufacturer's specifications. However, in order to cool the six cases of bottles (plastic bottle cases 70 in FIG. 3) from 72 °F (22 °C) to less than 40 F (4 °C), a substantially higher heat flow rate was required. To accomplish this, the third refrigeration loop 16 was closed and the first refrigeration loop 12 was opened. Then the compressor 20 in the first refrigeration loop 12 was started up to cool the first refrigerant medium, R-404a.
- the second refrigerant medium, HFE-7100 cooled by the first refrigerant medium via the first heat exchanger 26, in turn cooled (over a period of several hours) the thermal reservoir material 52 to the desired temperature of 20 °F (-7 °C).
- the first refrigeration loop 12 continued to operate and the third refrigeration loop 16 was opened.
- the second refrigerant medium was then circulated through the second heat exchanger 34 to transfer heat between the thermal reservoir 32 and the air circulation chamber 42 in the third refrigeration loop 16.
- TABLE 1 shows the thermal load (that is, heat transfer and temperature) data from this experiment as a function of time for a period of 42 minutes.
- Energy Rate from Air column indicate the rate of heat transfer in BTU/hr (watts) at a given time while the bottles are cooling to their desired temperature (approaching 32 °F or 0°C). Initially, this rate was over 40,000 BTU/hr (11700 W), roughly 7 times the capacity of the compressor 20 in the first refrigeration loop 12.
- the data listed under the "Energy Rate to Thermal Storage” column indicate the rate of energy adsorption by the thermal reservoir 32.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA01010795A MXPA01010795A (en) | 1999-04-26 | 1999-08-16 | Multistage rapid product refrigeration apparatus and method. |
AU55640/99A AU5564099A (en) | 1999-04-26 | 1999-08-16 | Multistage rapid product refrigeration apparatus and method |
JP2000613985A JP2002543363A (en) | 1999-04-26 | 1999-08-16 | Apparatus and method for multi-stage rapid product refrigeration |
EP99942211A EP1173716A1 (en) | 1999-04-26 | 1999-08-16 | Multistage rapid product refrigeration apparatus and method |
KR1020017013664A KR20010112461A (en) | 1999-04-26 | 1999-08-16 | Multistage Rapid Product Refrigeration Apparatus and Method |
BR9917272-0A BR9917272A (en) | 1999-04-26 | 1999-08-16 | Cooling system, and, multi-stage cooling process |
Applications Claiming Priority (2)
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US09/299,369 | 1999-04-26 | ||
US09/299,369 US6148634A (en) | 1999-04-26 | 1999-04-26 | Multistage rapid product refrigeration apparatus and method |
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WO2000065287A1 true WO2000065287A1 (en) | 2000-11-02 |
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PCT/US1999/018561 WO2000065287A1 (en) | 1999-04-26 | 1999-08-16 | Multistage rapid product refrigeration apparatus and method |
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US (1) | US6148634A (en) |
EP (1) | EP1173716A1 (en) |
JP (1) | JP2002543363A (en) |
KR (1) | KR20010112461A (en) |
AU (1) | AU5564099A (en) |
BR (1) | BR9917272A (en) |
MX (1) | MXPA01010795A (en) |
WO (1) | WO2000065287A1 (en) |
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- 1999-08-16 MX MXPA01010795A patent/MXPA01010795A/en unknown
- 1999-08-16 AU AU55640/99A patent/AU5564099A/en not_active Abandoned
- 1999-08-16 JP JP2000613985A patent/JP2002543363A/en active Pending
- 1999-08-16 KR KR1020017013664A patent/KR20010112461A/en not_active Application Discontinuation
- 1999-08-16 BR BR9917272-0A patent/BR9917272A/en not_active Application Discontinuation
- 1999-08-16 EP EP99942211A patent/EP1173716A1/en not_active Withdrawn
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Cited By (7)
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US10214292B2 (en) | 2006-02-03 | 2019-02-26 | Airbus Operations Gmbh | Cooling system using chiller and thermally coupled cooling circuit |
WO2009063055A1 (en) * | 2007-11-15 | 2009-05-22 | Shell Internationale Research Maatschappij B.V. | A method and apparatus for cooling a process stream |
WO2017005643A1 (en) * | 2015-07-08 | 2017-01-12 | Pfütze Uwe | Device and method for controlling the temperature of a medium |
CN107850350A (en) * | 2015-07-08 | 2018-03-27 | 乌维·帕福特兹 | Device and method for regulating the temperature of a medium |
US10690384B2 (en) | 2015-07-08 | 2020-06-23 | Uwe Pfütze | Device and method for controlling the temperature of a medium |
CN107850350B (en) * | 2015-07-08 | 2021-03-09 | 乌维·帕福特兹 | Device and method for regulating the temperature of a medium |
CN109340966A (en) * | 2018-11-14 | 2019-02-15 | 中国铁路设计集团有限公司 | A kind of dedicated heat recovery coil type air-cooled fluorine pump machine room Special air-conditioning device |
Also Published As
Publication number | Publication date |
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JP2002543363A (en) | 2002-12-17 |
BR9917272A (en) | 2002-01-15 |
AU5564099A (en) | 2000-11-10 |
US6148634A (en) | 2000-11-21 |
MXPA01010795A (en) | 2002-05-14 |
KR20010112461A (en) | 2001-12-20 |
EP1173716A1 (en) | 2002-01-23 |
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